JP2006139085A - Light shielding film and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for producing a light shielding film which has a black color tone, and is high in the optical density and small in the difference between thicknesses in an image part and a non-image part. <P>SOLUTION: The production method for the light shielding film uses a transferable silver complex salt as at least a portion of silver halide emulsion, and comprises diffusing the silver halide emulsion into an image receiving layer containing a silver deposition agent to form silver fine particles, then forming an image by exposing the image receiving layer, and removing the non-image part. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a light shielding film used in a display device such as a liquid crystal display device and a method for manufacturing the same.
The light shielding film for a display device referred to here is a black edge provided in a peripheral portion of a display device such as a liquid crystal, a plasma display, an organic EL, or a CRT, or the periphery of blue, red, or green pixels of these display devices The light shielding film is used as a black or black edge (black matrix) in the form of a lattice or stripe.

Several methods are known as a method for forming a light shielding film for a display device.
For example, the method of apply | coating the photosensitive resin composition containing carbon black is mentioned (refer patent document 1).
Although this method is low in production cost, since carbon black has a low optical density per unit coating amount, in order to ensure the same high light-shielding property as a metal film, the thickness of the carbon black-containing layer must be increased. I must. As a result, in the case of the black matrix, the overlap (step) between the black matrix and the pixel becomes large, the flatness of the color filter is deteriorated, the cell gap unevenness of the liquid crystal display element is generated, and display defects such as color unevenness are caused. There was a problem.
Further, when the RGB pixels are formed after the black matrix is produced by the method as described above, the RGB pixel formation surface is not flat, and thus defects (such as bubble generation) may occur when forming the RGB pixels.

On the other hand, a method using a metal film as a black matrix having a high light shielding property even with a thin film is known. For example, when a metal film such as chrome is used as the light shielding layer, the light shielding layer is formed by depositing a metal thin film by vapor deposition or sputtering, applying a photoresist on the metal thin film, and then forming a black matrix pattern. It is formed by exposing and developing the photoresist layer using a photomask having the same, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film (see, for example, Non-Patent Document 1 below) .
Since this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is small, but a vacuum film formation process or an etching process such as a vapor deposition method or a sputtering method is required, which increases the cost and burdens on the environment. There is a problem that it cannot be ignored. In addition, since it is a metal film, there is a problem that the reflectance is high and the display contrast is low under strong external light. For this, there is a means of using a low-reflective chromium film (such as one composed of two layers of metal chromium and chromium oxide), but it cannot be denied that the cost is further increased.

As described above, a black matrix that has a sufficient optical density even in a thin film, does not cause defects when forming colored pixels, and can be manufactured at low cost has not yet been provided.
JP-A-62-9301 Published by Kyoritsu Shuppan Co., Ltd. “Color TFT LCD”, pp. 218-220 (April 10, 1997)

  Accordingly, an object of the present invention is to provide a light-shielding film capable of obtaining a sufficient optical density even with a thin film, and an industrially advantageous production method thereof.

In view of such a situation, the present inventor has conducted earnest research. As a result, according to the following method, a light-shielding film can be obtained industrially advantageously, and a sufficient optical density can be obtained even if the light-shielding film is thin. The present invention has been completed.
That is, this invention provides the following method and the light shielding film obtained by this method.

  <1> At least a part of the silver halide emulsion as a transferable silver complex salt is diffused into an image receiving layer containing a silver depositing agent to form silver fine particles, and then the image receiving layer is exposed to form an image. Of manufacturing a light-shielding film for removing a portion.

  <2> A method of forming silver fine particles by diffusing at least a part of a silver halide emulsion as a transferable silver complex salt into an image receiving layer containing a silver depositing agent, and an emulsion containing a silver halide emulsion on the image receiving layer <1> The method for producing a light-shielding film according to <1>, wherein the layer and the image receiving layer are developed together, and then the emulsion layer is removed.

  <3> The method for producing a light shielding film according to <1> or <2>, wherein the light shielding film is a light shielding film for a color filter of a liquid crystal display device.

  <4> The method for producing a light shielding film according to <3>, wherein the light shielding film for the color filter is a black matrix.

  <5> A light-shielding film obtained by the production method according to any one of <1> to <4>.

  <6> A substrate for forming a light-shielding film, wherein an image-receiving layer containing a silver depositing agent is provided on the substrate.

  <7> The light-receiving film-forming substrate according to <6>, wherein the image-receiving layer contains a silver depositing agent in the photopolymerizable composition.

  <8> The substrate for forming a light-shielding film according to <6> or <7>, wherein the image-receiving layer contains silver fine particles.

  <9> A method of forming an image-like light-shielding film on a substrate, wherein an emulsion layer containing a silver halide emulsion is arranged adjacent to or in close proximity to a substrate having an image receiving layer containing a silver depositing agent, and developed Development in the presence of a liquid causes diffusion of at least a portion of the emulsion as a transferable silver complex salt into the image receiving layer to form silver fine particles, and then the image receiving layer is imagewise exposed to form a light-shielded image. A method for forming an image-like light-shielding film, comprising removing a non-image portion.

  <10> The method for forming an image-like light-shielding film according to <9>, wherein the emulsion layer is removed after the formation of silver fine particles.

  <11> A method for forming a color filter, in which an image-like light-shielding film is formed by the formation method according to <9> or <10>, and then a pixel is formed.

  The manufacturing method of the present invention does not require complicated operations and expensive equipment, and is an industrially advantageous method. The light shielding film for a display device obtained by this method has a sufficient optical density even if it is thin. And excellent in black hue.

  In the present invention, at least a part of the silver halide emulsion is made into a transferable silver complex salt and diffused into an image receiving layer containing a silver depositing agent to form silver fine particles, and then the image receiving layer is exposed to form an image, It is a manufacturing method of the light shielding film which removes an image part.

Hereinafter, the present invention will be described in more detail.
(substrate)
The image receiving layer in the present invention is usually provided on a substrate.
Although the board | substrate used for this invention is not specifically limited, The glass substrate used for a display apparatus etc. is preferable. As the glass substrate, a glass substrate using a known glass such as soda glass, low alkali glass or non-alkali glass can be used. The thickness of the substrate is preferably 0.5 to 3 mm, more preferably about 0.6 to 2 mm. As the glass substrate, for example, those described in “Introduction to liquid crystal display engineering (by Hanani Suzuki, published by Nikkan Kogyo Shimbun Co., Ltd. (1998))” can be used. A cycloolefin-based transparent polymer can also be used. The glass substrate and the plastic substrate are described, for example, on page 157 of “Reflective color LCD integrated technology (Tatsuo Uchida, CMC Co., Ltd., issued in 1999)”.

(Image receiving layer)
In the present invention, the image receiving layer is usually provided on a substrate. The image receiving layer contains at least a binder and a silver depositing agent.
Examples of the method for providing the image receiving layer on the substrate include the following methods.
A. A method in which an image-receiving layer coating solution is applied onto a substrate and dried.
B. A method of transferring an image receiving layer provided on a temporary support to a substrate.
Here, the thickness of the image receiving layer is preferably 0.05 to 20 [mu] m, particularly preferably about 0.05 to 0.5 [mu] m.

  In the present invention, a known photopolymerizable composition can be used for the image receiving layer. This photopolymerizable composition may contain a known polymer, monomer, photopolymerization initiator, and the like, and in particular, an alkali-soluble polymer is preferably used as a binder before polymerization. Specific examples of preferable photopolymerizable compositions include those described in JP-A-5-2107 [0021] to [0025].

<Image-receiving layer binder>
As the alkali-soluble polymer, a copolymer of acrylic acid and / or methacrylic acid and styrene or acrylate is preferable. As the acrylate, methyl methacrylate, ethyl acrylate, benzyl acrylate, benzyl methacrylate, 2-ethylhexyl acrylate and the like are preferable.
Specific examples of the alkali-soluble polymer include the following.
P-1: Acrylic acid / benzyl acrylate = 3/7 (Mn = 4000)
P-2: Methacrylic acid / benzyl acrylate = 4/7 (Mn = 3000)
P-4: Acrylic acid / benzyl acrylate / methyl methacrylate = 3/3/4
(Mn = 40000)
P-5: Acrylic acid / methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate = 2/2/3/3 (Mn = 9000)

The polyfunctional monomer is particularly preferably a polyfunctional acrylic monomer, and specific examples include the following.
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, 1-4 hexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

As the photopolymerization initiator, halomethyloxadiazole compounds, halomethyl-s-triazine compounds, and the like are preferable. Among them, bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate is preferable. These addition amounts are preferably in the following ranges in terms of mass% in the image receiving layer.
Alkali-soluble polymer: 10 to 50% by mass
Multifunctional monomer: 10 to 50% by mass
Photopolymerization initiator: 1 to 20% by mass

<Silver deposition agent>
The image receiving layer contains a silver depositing agent. This is a compound that helps the developing agent reduce the transferable silver complex salt in which the silver halide emulsion is dissolved to form silver fine particles. Specific examples of the silver depositing agent include heavy metals such as iron, lead, zinc, nickel, tin, copper, chromium and cobalt, and noble metals such as gold, silver (including colloidal silver), platinum and palladium. Further, noble metal sulfides and selenides, such as sulfides such as mercury, copper, zinc, silver and palladium, and selenides such as lead, zinc and antimony are also preferable silver depositing agents. Furthermore, since the silver halide previously applied is reduced by development to become metallic silver, it functions as a silver depositing agent.
The silver depositing agent is usually contained in the image receiving layer in the form of fine fine particles. The average particle size of the fine particles is 300 nm or less, preferably 2 to 60 nm. The coating amount of the silver depositing agent is preferably 0.005 to 0.2 g / m ² and particularly preferably 0.01 to 0.3 g / m ² .

The image receiving layer is formed by applying an image receiving layer coating solution onto a substrate. The image-receiving layer coating solution can be prepared, for example, by adding a silver depositing agent to the binder solution of the image-receiving layer, or by generating a silver depositing agent in the binder solution of the image-receiving layer.
The image receiving layer can also be provided by transferring the image receiving layer provided on the temporary support onto the substrate by lamination.

[Diffusion method of silver in the image receiving layer]
Examples of a method for forming silver fine particles by diffusing at least part of a silver halide emulsion as a transferable silver complex salt into an image receiving layer containing a silver depositing agent include the following methods.
(1) A method in which an image receiving layer and an emulsion layer are provided on a substrate by coating, and after development, the emulsion layer is removed.
(2) A material in which an emulsion layer is provided on a temporary support is prepared. Next, this material and the substrate on which the image receiving layer is provided are developed by overlapping with a developing solution, and then the emulsion layer is removed.
Of these two methods, the method (1) is preferred.
This method applies a so-called diffusion transfer method of silver salt photography.
In any of the methods (1) and (2), the image receiving layer and the emulsion layer can be provided by coating or lamination, and the step of removing the emulsion layer may be removed by dissolving the emulsion layer. The emulsion layer may be removed by peeling the emulsion layer from the image receiving layer.

(Silver halide emulsion, emulsion layer)
<Silver halide emulsion>
Examples of the silver halide emulsion used in the present invention include photosensitive silver halide emulsions used in the diffusion transfer method of silver salt photography. For example, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver iodochloride, silver chloroiodobromide, etc. can be used as the silver halide. In particular, silver iodobromide or silver chloroiodobromide having a silver iodide content of 1 to 10 mol% is preferred. The shape of the silver halide grains is not particularly limited, and cubic, octahedral, tabular, spherical, or a combination thereof can be used. The average grain size of the silver halide grains (expressed by the diameter when approximated to a sphere) is not particularly limited, but is preferably 4 μm or less, more preferably 0.2 to 2 μm. The photosensitive silver halide emulsion of the present invention may be chemically or spectrally sensitized by a known method.

The photosensitive silver halide emulsion used in the present invention is described by P. Glafkides, "Chemie et Phisique Photographique", published by Paul Montel (1967); GF Duffin, “Photographic Emulsion Chemistry”, published by Focal press (1966); VLZelikman et al, “Preparation and coating of photographic emulsions Making and Coating Photographic Emulsions) ”, published by Focal Press (1964), and the like. That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any method such as a one-side mixing method, a simultaneous mixing method, or a combination thereof. It may be used. A method (so-called back mixing method) in which particles are formed in an atmosphere containing excess silver ions can also be used. As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase produced by silver halide is kept constant, that is, a controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Furthermore, as a method for obtaining a tabular silver halide having a substantially uniform grain size, for example, the technique of US Pat. No. 4,797,354 can be used.
The photosensitive silver halide emulsion used in the present invention is described in detail in, for example, JP-A No. 5-45826, and the technique can be used.
In order to achieve an optical density as a light-shielding film, the amount of photosensitive silver halide in the emulsion layer of the present invention is about 0.3 to 7.0 g / m ² , preferably 1.0 to 5. It is about 0 g / m ² .

<Binder>
Gelatin is most preferred as the binder for the emulsion layer. As the gelatin, lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin or the like can be used. Furthermore, modified gelatin such as phthalated gelatin can also be used. Gelatin is described, for example, in “The Theory of the photographic Process” (published by Macmillan Publishing Co., Inc. (Macmillan Publishing)) by THJames.
In addition to gelatin, proteins such as casein and albumin, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, and synthetic polymers such as polyvinyl alcohol and polyvinyl pyrrolidone can be used as the binder for the emulsion layer.

In addition to the binder and the silver halide emulsion, a hardener, a coating aid (surfactant), a dye, an ultraviolet absorber and the like may be added to the emulsion layer as necessary. Specific examples of these compounds are described, for example, in JP-A-5-45826.
The film thickness of the emulsion layer is preferably 0.3 to 30 μm, particularly preferably about 1.0 to 10 μm.

As a method of providing an emulsion layer on an image receiving layer or a temporary support, a method of coating and drying an emulsion layer coating solution containing the silver halide emulsion or binder on the image receiving layer or the like is used. A method of drying after coating the emulsion layer coating solution is preferred. As a coating method, a known method known in the field of silver salt photography can be used.
In addition, as a method of providing an emulsion layer on an image receiving layer or the like by laminating, an emulsion layer provided on a temporary support is used, and this is laminated on an image receiving layer and transferred. At this time, in order to perform good lamination, it is preferable to provide a thermoplastic resin layer between the temporary support and the emulsion layer.
Examples of the temporary support include polyesters such as polyethylene terephthalate and polynaphthalene terephthalate, cellulose derivatives such as cellulose triacetate, polyolefins such as polyethylene and polypropylene, paper coated with polyethylene, and sheets such as polystyrene. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the temporary support is preferably 5 to 300 μm, particularly preferably about 20 to 200 μm. Those having a thickness of 300 μm or more are disadvantageous in cost, and those having a thickness of less than 5 μm may not have sufficient strength.

  Furthermore, the resin constituting the thermoplastic resin layer is not necessarily essential, but is desirably alkali-soluble. In this case, as a resin constituting the thermoplastic resin layer, a saponified product of ethylene / acrylic acid ester copolymer, a saponified product of styrene / (meth) acrylic acid ester copolymer, styrene / (meth) acrylic acid / (meta ) Acrylic acid ester terpolymers, saponified products of vinyl toluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, (meth) acrylic acid such as (meth) acrylic acid butyl and vinyl acetate Among saponified products such as ester copolymers, and organic polymers by “Plastic Performance Handbook” (published by Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, Industrial Research Committee, published October 25, 1968), At least one kind can be appropriately selected from those soluble in an alkaline aqueous solution.

These resins are preferably used by mixing two types of resins A and B as follows. That is,
Among the above resins, a resin having a weight average molecular weight of 50,000 to 500,000 (glass transition temperature Tg = 0 to 140 ° C.) (hereinafter, also referred to as “resin A”) is preferably weight average molecular weight 6 What was selected from resin in the range of 10,000 to 200,000 (Tg = 30 to 110 ° C.) can be used.

  Specific examples of the resin A include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, and JP-B-59-44615. JP-A-54-92723, JP-A-54-99418, JP-A-54-137085, JP-A-57-20732, JP-A-58-93046, JP-A-59-97135, No. 60-159743, OLS 3254254, JP-A-60-247638, JP-A-60-208748, JP-A-60-214354, JP-A-60-230135, JP-A-60-258539, JP-A-61-169829, JP-A-61-213213, JP-A-63-147159, JP-A-63-213837, JP-A-63-26644 JP-A-64-55551, JP-A-64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-2-208602. Resin soluble in an alkaline aqueous solution described in each specification (publication) of No. -39653. Particularly preferred is a methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

  Among the above-mentioned various resins, a weight average molecular weight is preferably from a resin (hereinafter also referred to as “resin B”) having a weight average molecular weight of 3,000 to 30,000 (Tg = 30 to 170 ° C.). A resin selected from resins in the range of 4,000 to 20,000 (Tg = 60 to 140 ° C.) can be used. Preferable specific examples of the resin B can be selected from those described in the respective specifications (gazettes) cited as specific examples of the resin A, and particularly preferably, Japanese Patent Publication No. 55-38961, It is a styrene / (meth) acrylic acid copolymer described in 241340.

  If the weight average molecular weight of the resin A constituting the thermoplastic resin layer is less than 50,000 or Tg is less than 0 ° C., reticulation occurs and the thermoplastic resin protrudes to the periphery during transfer. Permanent support may be significantly contaminated. Further, if the weight average molecular weight of the resin A exceeds 500,000 or the Tg exceeds 140 ° C., bubbles may enter between pixels at the time of transfer, or the alkaline aqueous solution removability of the thermoplastic resin may be significantly reduced.

  When the weight average molecular weight of the resin B constituting the thermoplastic resin layer is less than 3,000 or the Tg is less than 30 ° C., reticulation occurs and the thermoplastic resin protrudes to the periphery during transfer. Permanent support may be significantly contaminated. If the weight average molecular weight of the resin B exceeds 30,000 or the Tg exceeds 170 ° C., bubbles may enter between pixels during transfer, or the ability of the thermoplastic resin to remove an alkaline aqueous solution may deteriorate.

  In the mixing ratio when the resins A and B are mixed, the ratio of the resin A to the total mixed mass is preferably 5 to 95% by mass. If the ratio of the resin A exceeds 95%, bubbles may easily enter between pixels during transfer. If the ratio is less than 5%, the thermoplastic resin may protrude into the surroundings, or the thermoplastic resin layer may become brittle and cut. Fine chips may be easily scattered in the process.

  For the purpose of adjusting the adhesive force and / or transferability with the temporary support, the thermoplastic resin layer includes various resins, supercooling substances, adhesion improvers, surfactants, release agents, etc. together with the above resins. By adding a plasticizer, the Tg of the thermoplastic resin layer can be finely adjusted.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono (meta) ) Addition reaction product with acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of over bets of a condensation product of bisphenol A and polyethylene glycol mono (meth) acrylate.

  The addition amount of the plasticizer is preferably 0 to 200% by mass and more preferably 20 to 100% by mass with respect to the total amount (mass) of the resins A and B constituting the thermoplastic resin layer.

  The thickness of the thermoplastic resin layer is preferably 6 μm or more. The reason for this is that if the layer thickness of the thermoplastic resin is less than 6 μm, it is impossible to completely absorb the unevenness of the foundation of 1 μm or more. The upper limit of the layer thickness is about 100 μm or less, preferably about 50 μm or less, from the viewpoint of the ability to remove alkaline aqueous solution and suitability for production.

  When preparing a coating solution for forming a thermoplastic resin layer, a solvent is generally used, and the solvent can be used without particular limitation as long as the resin constituting this layer is dissolved. For example, methyl ethyl ketone, n-propanol, i-propanol etc. are mentioned.

[developing]
The development method is not particularly limited, and a method of developing a silver halide photographic material by a diffusion transfer method can be used.
The developer contains a developing agent, an alkaline agent, and a silver solvent. Hydroquinone as the developing agent. Known developing agents such as amidol, metol, hydroxylamine, N-methylhydroxylamine, triethanolamine can be used. As the alkali agent, a known alkali agent such as sodium hydroxide or potassium hydroxide can be used. As the silver solvent, a known silver solvent can be used in silver halide photographic materials for diffusion transfer such as sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate, uracil and the like.
If necessary, the developer may be added with an antifogging agent or a stabilizer well known in the silver halide photographic material of the diffusion transfer method.
Regarding the developing method, the method of developing a silver halide photographic material by the diffusion transfer method can be used without any particular limitation. A developing solution and a developing method in the diffusion transfer method are described in detail in paragraphs 0047 to 0053 of JP-A-5-45826.

The transferable silver complex salt in the present invention is a complex salt of a known silver halide and a silver solvent contained in a developing solution in a silver halide photographic material of a diffusion transfer method. When at least a part of the silver halide is made into a transferable complex salt with a silver solvent and the complex salt is diffused into the image receiving layer, the complex salt is reduced to silver atoms by the action of the developing agent contained in the developer, and this is the image receiving layer. It deposits on the silver deposition nuclei (fine particles made of silver deposition agent) to form a silver image. The silver depositing agent in the image receiving layer accelerates the reduction reaction.
The silver image of the present invention is usually about 5 to 2000 nm in size. The color tone of the silver image is preferably black, and for this purpose, a color tone agent may be added to the emulsion, emulsion layer, image receiving layer and developer. As the color toning agent, those known by the diffusion transfer method of silver salt photography can be used.

[Removal of emulsion layer]
The removal of the emulsion layer includes a method of peeling off the emulsion layer and a method of dissolving and removing the emulsion layer, but are not limited thereto. Specific examples of the method for peeling the emulsion layer include a method in which a release layer containing a silicone resin or the like as a binder is previously provided between the emulsion layer and the image receiving layer. In addition, the method for dissolving and removing the emulsion layer includes a method of treating the emulsion layer with an aqueous solution such as papain (proteolytic enzyme) or hypochlorous acid, followed by washing. It is done.

[exposure]
The image receiving layer on which the silver image has been formed as described above can be made into a light-shielding film by patternwise exposure and alkali development.
The light source used for exposure is selected according to the photosensitivity of the photosensitive resin layer of the image receiving layer. For example, a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or an argon laser can be used. As described in JP-A-6-59119, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used in combination. Similarly, as described in JP-A-6-59119, if necessary, the light transmittance in the photosensitive wavelength region of the image receiving layer of red, green, and blue pixels formed on the substrate in advance is set to 2%. The following may be used.

[Alkali development]
As the developer for the image-receiving layer, a dilute aqueous solution of an alkaline substance is used, but a solution containing a small amount of an organic solvent miscible with water may be used. Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Mention may be made of morpholine, tetraalkylammonium hydroxides (for example tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01 to 30% by weight, and the pH is preferably 8 to 14.

  Suitable organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the organic solvent miscible with water is generally 0.1 to 30% by weight.

A known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01 to 10% by weight.
Development can be performed by immersing the image receiving layer or the like in a developer for 5 to 600 seconds.

  The developer can be used as a bath solution or a spray solution. Development can be performed by immersing the image receiving layer or the like in a developer for 5 to 600 seconds. In order to remove the uncured portion of the light-shielding photosensitive resin composition layer in a solid state (preferably in the form of a film), a method such as rubbing with a rotating brush or a wet sponge in the developer, or spraying the developer A method of using the spraying pressure at the time is preferable. The temperature of the developer is usually preferably in the range of about room temperature to 40 ° C. It is also possible to put a water washing step after the development processing.

[Black Matrix]
Next, the black matrix of the present invention will be described.
As described above, the black matrix of the present invention can be used for a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, etc. Among them, it is particularly preferable to use it for a liquid crystal display device.
The black matrix preferably has a thickness of 0.1 to 0.8 μm, more preferably 0.2 to 0.6 μm. When the thickness is less than 0.1 μm, the light-shielding property is lowered, and when the thickness exceeds 0.8 μm, the surface of red, blue, and green pixels to be provided thereafter is not smooth and color unevenness occurs.

The optical density of the black matrix is preferably 3.0 or more, more preferably 3.5 or more. When the optical density is less than 3, the contrast is lowered and the display quality is lowered.
Although there is no restriction | limiting in particular in the volume fraction of the core-shell fine particle in a black matrix, Usually, 5 to 70%, More preferably, the range of about 10 to 50% is desirable. If the volume fraction is less than 5%, the necessary light shielding properties cannot be obtained, and if it exceeds 70%, the black matrix becomes brittle.
In the case of the black matrix of the present invention, performances such as heat resistance, light resistance, chemical resistance, surface smoothness and hardness generally required for a color filter are required. For details on the required performance, see page 189 of “Color Filter Deposition Technology and Chemicals (Sequentially Supervised by Watanabe, CMC Co., Ltd., published in 1998)”, “Next Generation Liquid Crystal Display Technology (Tatsuo Uchida, Industrial Research Committee, 1994) Issued) ”on page 117. The necessary performance can be controlled by the pigment / binder ratio, binder type, exposure and heat treatment conditions, etc., as in the known black matrix.

[Color filter]
The color filter of the present invention is a substrate provided with the black matrix of the present invention and further provided with pixel groups exhibiting two or more colors, for example, red, blue and green pixel groups.
There is no particular limitation on the method of forming the pixel group. Known methods such as a photolithography method, an etching method, and a printing method can be used. These methods are described in, for example, “Film Filter Film Formation Technology and Chemicals (supervised sequentially by Watanabe, CMC Co., Ltd., published in 1998)”.

Of these methods, the photolithography method is preferable. Specific methods include the following.
The first is a method using a resist solution containing a pigment or a dye. In this method, first, a resist is applied to a substrate, dried, exposed through a photomask, and then developed to create a color filter.
The second is a method using a transfer material having a transfer layer containing a pigment or dye. In this method, first, a transfer material is laminated on a substrate, exposed through a photomask, and then developed to form a color filter.

The arrangement method (BRG pixel pattern) of the pixel group of the color filter of the present invention is not particularly limited, and the arrangement method is a general black matrix shape such as a stripe shape, a lattice shape, a delta array shape, a block shape, or a checkered shape. Can be used. A TFT type in which the pixel has an uneven shape can also be used. These arrangement methods are described, for example, on page 14 of “Color Filter Film Formation Technology and Chemicals” (supervised sequentially by Watanabe, CMC Co., Ltd., issued in 1998).
The chromaticity range of the color filter of the present invention is the same as that of the conventional color filter. The chromaticity range and related backlights are also described, for example, on page 15 of the aforementioned “Color filter deposition technology and chemicals (supervised sequentially by Watanabe, CMC Co., Ltd., issued in 1998)”.

  In the case of the color filter of the present invention, the heat resistance, light resistance, chemical resistance, surface smoothness, hardness and the like described for the black matrix are required.

[Display device]
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, see “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd., 1990)
) ”,“ Display devices (written by Junaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989) ”
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. For example, “Next generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”
It is described in. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. A color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center).

In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The black matrix of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shimadzu Co., Ltd., issued by 1994)”, “2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute published in 2003)
It is described in.

[Target use]
The black matrix of the present invention can be applied to applications such as portable terminals such as televisions, personal computers, liquid crystal projectors, game machines, and mobile phones, digital cameras, and car navigation systems without particular limitation.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Example 1
[Formation of image receiving layer]
(Image-receiving layer coating solution 1)
Methyl alcohol 40.0g
Methyl ethyl ketone 40.0g
F176PF (solid content 20%) (fluorine surfactant manufactured by Dainippon Ink & Chemicals, Inc.)
0.1g
0.001 g of hydroquinone monomethyl ether
Dipentaerythritol hexaacrylate 15.0g
Benzyl methacrylate / methacrylic acid = 7/3
25.0 g of polymer A having a number average molecular weight of about 3000
Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.1 g

The following solution A was added to the above (image-receiving layer coating solution 1), and solution B was added at a rate of 1 ml / second while stirring was continued. After the addition, stirring was continued for 5 minutes to obtain an image-receiving layer coating solution. In this coating solution, 7 × 10 ⁻³ mmol of palladium sulfide is produced per 1 g of cellulose acetate in calculation.
Solution A: Mixture of 16 ml of 0.0175 M sodium sulfide / 9-hydrate solution and 24 ml of acetone Solution B: Mixture of 4 ml of 0.70 M palladium tetrachloride / sodium / trihydrate solution and 36 ml of methanol

(Formation of image receiving layer)
The image-receiving layer coating solution was applied on a glass substrate so that the dry film thickness was 0.3 μm, and dried at 80 ° C. for 5 minutes.

[Formation of emulsion layer]
(Emulsion layer coating solution)
Photosensitive silver halide emulsion (silver iodobromide emulsion having an average grain size of 1.1 μm and AgI = 3 mol%)
9.8g
Gelatin 14.4g
Sensitizing dye A (Formula (A) below) 3.2 × 10 ⁻³ g
Sensitizing dye B (Formula (B) below) 3.2 × 10 ⁻³ g
Sensitizing dye C (Formula (C) below) l. 2 × 10 ⁻³ g
Surfactant (Sandet BL (manufactured by Sanyo Chemical Co., Ltd.)) 0.05g
980 g of distilled water

(Emulsion layer formation)
The above coating solution was applied onto a glass substrate on which an image receiving layer was formed so that the silver coating amount was 2.2 g / m ² and dried at 30 ° C. for 5 minutes.

[Diffusion and development]
Development was performed by immersing the sample in the following developer. Development was performed at 10 ° C. for 60 seconds.

(Developer formulation)
Potassium hydroxide 180g
Uracil 88g
Anhydrous sodium thiosulfate 1.0 g
Potassium iodide 0.3g
Triethanolamine 0.5g
250 g of N, N-bis (methoxyethyl) hydroxylamine (17% aqueous solution)
Tetrahydropyrimidinethione 0.2g
2,4-Dimethylmercaptopyridine 0.2g
Sodium 3- (5-mercaptotetrazolyl) benzesisulfonate 0.2 g
3.0 g of 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidine
1270 ml of distilled water

[Removal of emulsion layer]
The developed sample was washed with distilled water at 43 ° C. to remove the emulsion layer, and then dried at 25 ° C. for 60 minutes.

[Exposure, development]
An exposure of 500 mJ / cm ² was performed from the coated surface side using an ultrahigh pressure mercury lamp. Next, development processing (33 ° C., 20 seconds) was performed using a developing solution TCD (manufactured by Fuji Photo Film Co., Ltd., alkali developer) to remove the image receiving layer in the unexposed portion. Thereafter, the film was dried at 100 ° C. for 2 minutes, and then heat-treated at 220 ° C. for 40 minutes.
In this way, a light shielding film was obtained.

[Evaluation results]
The optical density of the light shielding film thus obtained was measured and found to be 3.5. Moreover, the color tone was black and it was a favorable light shielding film.

  The method of the present invention is simple, and the light-shielding film produced is preferable as a light-shielding film having a black color tone and high optical density. Further, the difference in thickness between the image area and the non-image area is small, which is desirable as a light shielding film.

Claims (11)

  At least a part of the silver halide emulsion is made into a transferable silver complex salt and diffused into an image receiving layer containing a silver depositing agent to form silver fine particles. Then, the image receiving layer is exposed to form an image, and then the non-image area is removed. A method of manufacturing a light shielding film.   A method of forming silver fine particles by diffusing at least a part of a silver halide emulsion as a transferable silver complex salt into an image receiving layer containing a silver depositing agent, and an emulsion layer containing a silver halide emulsion on the image receiving layer and 2. The method for producing a light-shielding film according to claim 1, wherein the image-receiving layer is developed together and then the emulsion layer is removed.   3. The method for producing a light shielding film according to claim 1, wherein the light shielding film is a light shielding film for a color filter of a liquid crystal display device.   4. The method for producing a light shielding film according to claim 3, wherein the light shielding film for the color filter is a black matrix.   The light shielding film obtained by the manufacturing method of any one of Claims 1-4.   A substrate for forming a light-shielding film, wherein an image-receiving layer containing a silver depositing agent is provided on the substrate.   7. The light-shielding film-forming substrate according to claim 6, wherein the image-receiving layer contains a silver depositing agent in the photopolymerizable composition.   8. The light-shielding film-forming substrate according to claim 6, wherein the image-receiving layer contains silver fine particles.   A method for forming an image-like light-shielding film on a substrate, wherein an emulsion layer containing a silver halide emulsion is disposed adjacent to or in close proximity to a substrate having an image receiving layer containing a silver depositing agent, and the presence of a developer Development is performed below to diffuse at least a portion of the emulsion as a transferable silver complex salt into the image receiving layer to form silver fine particles, and then the image receiving layer is imagewise exposed to form a light-shielded image, and then a non-image portion. A method for forming an image-like light-shielding film, wherein   10. The method for forming an image-like light-shielding film according to claim 9, wherein the emulsion layer is removed after the silver fine particles are formed.   A method for forming a color filter, wherein an image-like light-shielding film is formed by the formation method according to claim 9, and then pixels are formed.